Bacterial light source with high quality of light

ABSTRACT

A light source for emitting emitted light having an SPD comprising: (a) a plurality of light emitters including at least one violet solid-state emitter; (b) at least one phosphor; wherein said light emitters and said at least one phosphor being configured such that: at least 25% of the power within the SPD is in the range 390-420 nm, and the emitted light has a chromaticity which is within a Duv distance of less than 5 points from the Planckian locus.

REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. application Ser. No.15/633,425, filed Jun. 26, 2017, which is based on U.S. ProvisionalApplication No. 62/354,464, filed Jun. 24, 2016, hereby incorporated byreference in its entirety.

FIELD OF INVENTION

The present invention relates, generally, to a light source, and, morespecifically, to a bactericidal light source with a high quality oflight.

BACKGROUND

It has recently been discovered that a high flux of illumination by 405nm radiation could have a significant desirable bactericidal effect.Following this, some companies have proposed creating a white lightemitter having a large violet peak, which could providegeneral-illumination light at the same time as a bactericidal effect.The conventional approach is to combine standard white light emittingdiodes (LED)s with violet LEDs emitting at 405 nm.

Applicants recognize, however, that this approach leads to light havingpoor chromaticity. Chromaticity may be quantified through use theCartesian distance in (u v) space, known as Duv, or in (x y) space,known as Dxy. For a target chromaticity (for instance, that of aBlackbody radiator at 3000 K), Duv is calculated as the Cartesiandistance between that target chromaticity and the light source's actualchromaticity in (u, v) space. In some cases, the distance is computedbetween a point and a curve—for instance, between the chromaticity of aspectrum (a point) and the Planckian locus (a curve). The distance isthe closest distance from the point to the curve (i.e. the distance fromthe point to its orthogonal projection on the curve, in the space ofinterest). This concept is commonly used in color science to express howclosely an SPD replicates the chromaticity of a blackbody radiator.Color distances may be expressed in values of Duv or Dxy. As known, Duvand Dxy are related. Typically, a Duv value is about half of thecorresponding Dxy value (with some variation depending on the specificdirection of the color shift). In particular, for shifts substantiallyalong the +/−y direction (as is the case in some embodiments shownherein), this ratio is 0.5. This conversion factor may be used totranslate from one distance metric to the other.

FIGS. 1a and 1b illustrate the poor chromaticity of the conventionalapproach of combining standard white light emitting diodes (LED)s withviolet LEDs emitting at 405 nm. In FIG. 1a , light emitted from astandard white LED (white spectrum 102, on-Planckian with correlatedcolor temperature (CCT)=3000 K, Ra=80, R9˜0) is combined with a largeviolet peak from a violet LED (violet spectrum 104, having a peak at 405nm). The resulting spectrum 106 (has a high violet content, and may besuitable for bactericidal purposes. However, the addition of the violetpeak pulls the chromaticity to a higher CCT (3200K) and farbelow-Planckian (Duv=−0.0177), resulting in an uncontrolled verypronounced pink tint.

Furthermore, depending on the amount of violet light, the resultingchromaticity may occur at any uncontrolled color point, which can beundesirable in applications where a controlled chromaticity (often,substantially on-Planckian) is wanted. This is further illustrated inFIG. 1b . FIG. 1b shows the chromaticity (in x-y diagram) of the samestandard white LED, when combined with various amounts of violet light.Curve 108 is the Planckian locus. The percent values shown on FIG. 1bcorrespond to the violet fraction, i.e. the fraction of the spectralpower distribution (SPD) in the range 390-420 nm. At 0% violet, thesource is on-Planckian. In other words, a standard white LED comprising0% violet is on-Planckian. As the violet fraction increases to 10%, 20%,and 30%, however, the chromaticity is pulled below-Planckian, and theemitted light is no longer white. This is characterized by the Duvdistance from the Planckian locus—i.e., −0.0044, −0.0102 and −0.0177,respectively.

The large values of Duv distance from Planckian demonstrate that it isnot possible to add much violet light and remain near the Planckianlocus with this approach, while emitting white light. The last point ofFIG. 1b has 30% violet, and corresponds to the SPD of composite spectrum106 of FIG. 1a . Therefore, there is a need for a light source with aspectrum having a large fraction of violet light but retaining desirablequality of white light. The present invention fulfills this need amongothers.

SUMMARY OF INVENTION

The following presents a simplified summary of the invention in order toprovide a basic understanding of some aspects of the invention. Thissummary is not an extensive overview of the invention. It is notintended to identify key/critical elements of the invention or todelineate the scope of the invention. Its sole purpose is to presentsome concepts of the invention in a simplified form as a prelude to themore detailed description that is presented later.

Applicants have found that it is possible to design particular spectra,through a careful configuration of LEDs and phosphor formulations, whichcan provide a large fraction of violet light together with high qualityof light. For example, it is known that in some cases, an SPD having acontrolled amount of violet light can yield desirable properties forquality of light. For instance, a violet amount of 3-10% for a spectrumat 3000K can increase the color rendering index (CRI) and can improvethe rendition of whiteness for objects having fluorescing agents.

Although Applicants have determined the need for a light source, whichhas a spectrum having a large fraction of violet light, but whichretains desirable quality of light, the desirability of this is type oflight source is generally contrary to conventional thinking.Specifically, one skilled in the art of LED lighting would typically notdesign an LED whose spectrum has such a large amount of violet light.Indeed, the human eye is much less sensitive to violet light than it isto blue light. As a result, when the amount of violet light in aspectrum is increased, the luminous efficacy of radiation (LER) of theresulting spectrum decreases. LER quantifies the lumens per opticalwatts in the SPD, and describes how brightly an SPD is perceived by ourvision system. A common goal of LED lighting is to increase LER.

To achieve a white spectrum having a high LER, the natural choice is toinclude blue light in the spectrum, and to either have no violet lightwhatsoever (conventional approach of blue-pumped LED with phosphorconversion) or to retain a small fraction of violet light (typically3-10% for warm-white light sources) to improve color rendition withoutexceedingly decreasing LER. Therefore, increasing the violet fraction toa very high value is contrary to common practice in efficient LEDlighting. A slightly higher fraction of violet light may be suitable fora higher-CCT light source, however, for common CCTs (in the range2700K-6000K) the violet fraction remains moderate in general lightingapplications.

Accordingly, one aspect of the invention is a spectrum having arelatively high component of violet light (around 405 nm) in the finalspectrum. By varying the amount of violet and blue radiation a desiredchromaticity and violet fraction can be achieved. The violet componentcan be calculated by computing the fraction of the SPD which falls inthe violet range. This can be expressed in different ways, including apercent of the total power in the SPD. In one embodiment, the violetrange is 390 nm-420 nm. Therefore, the “violet fraction” in thefollowing will be computed as the ratio of the power of the SPD in therange 390-420 nm, to the total power of the SPD (in practice, for LEDsources, the total power can often be computed by considering the range380-780 nm since very little radiation lies outside this range). Anotherway to quantify bactericidal effects is in terms of watts per lumens:this quantifies how many watts fall in the violet range of interest (forinstance, 390-420 nm) for a spectrum emitting one lumen of light.

Furthermore, Applicants recognize that traditional color matchingfunctions (CMFs) used to calculate chromaticity, and thus to target aspectrum's proximity to the Planckian locus, are inaccurate forspectrums having a large component of violet. Specifically, Applicantsconducted experiments which demonstrate that the original CIE 1931 2°CMFs are not as accurate as 10° CMFs, especially at short wavelengths.For example, using the 1964 10° CMFs yielded a much better perceptualmatch of chromaticity. In other words, if a source having a large violetfraction is designed to be on-Planckian (at a given CCT) according tothe 10° CMFs, this source has a perceived chromaticity which is close toa blackbody radiator (i.e. a filament lamp) at the same CCT. Incontrast, if color targeting is performed with 2° CMFs, the perceivedchromaticity may have a pronounced pinkish tint. Therefore, unlessotherwise specified, chromaticity is calculated using CIE 1964 10° CMFsbecause of its accuracy at shorter wavelengths.

In one embodiment, the invention relates to a light source for emittingemitted light having an SPD comprising: (a) a plurality of lightemitters including at least one violet solid-state emitter; (b) at leastone phosphor; wherein said light emitters and said at least one phosphorbeing configured such that: at least 25% of the power within the SPD isin the range 390-420 nm, and the emitted light has a chromaticity whichis within a Duv distance of less than 5 points from the Planckian locuscalculated using 1964 10° CMFs.

In another embodiment, the invention relates to a light source foremitting emitted light having an SPD comprising: a plurality of lightemitters including at least one violet solid-state emitter; and at leastone phosphor; wherein the light emitters and said phosphor areconfigured such that: the SPD is characterized by a ratio of power inthe range 390-420 nm to lumens which is above 0.5 mW/lm, and the emittedlight has a chromaticity which is within a Duv distance of less than 5points from the Planckian locus calculated using 1964 10° CMFs.

In yet another embodiment, the invention relates to a method of reducingbactericidal counts, the method comprising: (a) powering a light sourceto emit emitted light having a chromaticity, said light sourcecomprising a plurality of light emitters including at least one violetsolid-state emitter and at least one phosphor, herein said chromaticityis within a Duv distance of less than 5E-3 from the Planckian locuscalculated using 1964 10° CMFs; and (b) configuring said light source toilluminate a surface with said emitted light to reduce a bacterial countby at least a factor of ten in twelve hours.

BRIEF DESCRIPTION OF FIGURES

FIGS. 1a and 1b illustrate a spectrum and corresponding chromaticitygenerated by the combination of different types of LEDs according to oneor more embodiments of the invention.

FIGS. 2a , and 2B illustrate spectra generated by various combinationsof LEDs according to one or more embodiments of the invention.

FIG. 3 illustrates spectrum generated by a laser LED and at least oneother LEDs according to one or more embodiments of the invention.

FIGS. 4a -4C illustrate various light source configurations according toone or more embodiments of the invention.

FIG. 5 illustrates a cross-section of the epitaxial layers of an LEDaccording to one or more embodiments of the invention.

FIG. 6a-6d illustrate the spectral power distributions according to oneor more embodiments of the invention.

FIGS. 7-8 illustrate the spectral power distributions according to oneor more embodiments of the invention.

FIGS. 9-11 illustrate color metrics versus correlated color temperatureaccording to one or more embodiments of the invention.

FIG. 12 illustrates the spectral power distribution according to one ormore embodiments of the invention.

FIG. 13 illustrates the violet content as related to correlated colortemperature according to one or more embodiments of the invention.

FIG. 14 illustrates a spectrum corresponding to the combination of oneor more types of LEDs according to one or more embodiments of theinvention.

FIG. 15 illustrates experimental results of violet light on bacteriaaccording to one or more embodiments of the invention.

FIG. 16 illustrates experimental results of white light on bacteriaaccording to one or more embodiments of the invention.

FIG. 17 illustrates the tradeoffs in spectral power distribution basedon the amount of violet and blue radiation according to one or moreembodiments of the invention.

FIGS. 18a-18b illustrate spectral power distributions having varyingviolet contents according to one or more embodiments of the invention.

FIG. 19 illustrates a light source according to one or more embodimentsof the invention.

FIG. 20 is a graph illustrating the difference between various CMFsaccording to one or more embodiments of the invention.

DETAILED DESCRIPTION

FIG. 19 illustrates an embodiment of light source 1900 for emittingemitted light having a spectral power distribution. In the illustratedembodiment, the light source 1900 includes a plurality of light emitters1902 and at least one phosphor 1906. The plurality of light emitters1902 has at least one violet solid-state emitter 1904. In oneembodiment, the plurality of light emitters 1902 and the at leastphosphor 1906 are configured such that at least 25% of the power withinthe SPD is in the rage of 390-420 nm, and the emitted light has achromaticity which is within a Duv distance of less than 5E-3 from thePlanckian locus, as calculated with 1964 10° CMFs. In anotherembodiment, the plurality of light emitters 1902 and the at leastphosphor 1906 are configured such that the SPD is characterized by aratio of power in the range of 390-420 nm to lumens which is above 0.5W/lm, and the emitted light has a chromaticity which is within a Duvdistance of less than 5 points from the Planckian locus. In yet anotherembodiment, the plurality of light emitters 1902 and the at leastphosphor 1906 are configured such that at least 15% of the power withinthe SPD is in the range of 390-420 nm, and a first distance of the SPD'schromaticity to the Planckian locus computed with 1931 2° CMFs isgreater than a second distance of the SPD's chromaticity to thePlanckian locus calculated using CIE 1964 10° CMFs.

While the embodiment of FIG. 19 illustrates that the at least phosphor1906 is disposed over each of the plurality of lights emitters 1902, inone more embodiments, at least one of the plurality of emitters 1902 maybe disposed outside that at least one phosphor 1906 such that lightemitted by the light source is not converted by the phosphor. Further,in other embodiments, each of the plurality of light emitters 1902 maybe coupled to discrete a phosphor or phosphors. In such embodiment, oneor more of the plurality of light emitters 1902 may not be coupled to aphosphor.

In one embodiment, the plurality of light emitters 1902 may be anysuitable light emitters able to obtain a desired SPD. For example, theplurality of light emitters 1902 may be solid state emitters (LEDs orLasers). Different light emitters at different wavelengths may be used.At least one emitter may have a peak wavelength around 405 nm or in arange 400-410 nm or 395-415 nm, to provide bactericidal effect. At leastone emitter may have a peak wavelength in a blue range (or in a range430-490 nm or 440-460 nm). Further, the at least one phosphor 1906 mayinclude any number and type of phosphors (luminescent materials) able toobtain a desired SPD, including blue, green, yellow and red phosphors.The phosphors may be configured to convert light from some of all lightemitters, for instance they absorb violet light but no blue light orvice-versa.

Various aspects of quality of light are addressed below, including:correlated color temperature (CCT); distance from the Planckian locus(Duv); chromaticity of the light (including perceptual chromaticity);color rendering index (CRI) (general index Ra and special red index R9);IES TM-30-15 color metrics (including Rf, Rg, and special indices suchas the red rendering index Rfh1); Cyanosis Observation Index (COI) (asdescribed in document AS/NZS 1680.2.5:1997).

Although the range 390-420 nm is illustrated herein, it should beunderstood that, in various embodiments, other ranges centered at ornear 405 nm are also suitable. In other embodiments, the violet range is400-410 nm, 400-420 nm, 400-430 nm, 380-430 nm. In some embodiments, apreferred peak wavelength is selected (such as 400 nm, 405 nm, 410 nm,415 nm, 420 nm, 425 nm) and the violet range is a window of +/−1 nm or 2nm or 5 nm or 10 nm or 15 nm or 20 nm around this peak. Further, theviolet content may be quantified various different ways. (e.g., byintegrating the violet light with a bactericidal action spectrum, whichmay peak around 405 nm). One skilled in the art will know to translatethe following teachings to a different quantification of violet content,in order to design new spectra having a large violet content and a highquality of light. Accordingly, as the science of bactericidal effects ofviolet light is refined, improvements to the spectrum's detailed violetcontent are envisioned, and can benefit from the present teachings.

On-Planckian Sources with a Large Violet Fraction

The term white chromaticity qualitatively describes light having a whiteappearance. This can be quantified in several ways. In variousembodiments, white light is light along the Planckian (Blackbody) locusor along the locus of CIE daylight. In some embodiments, white light islight having chromaticity coordinates within an ANSI quadrangle orMacAdam ellipse defining white light [as described in ANSI C78.2772015]. In other embodiments, white light is light slightly below theBlackbody locus, along the “white locus” studied by researchers at RPI.The RPI white locus is a curve in the x-y coordinate space which isdistinct from the Blackbody locus. It may be used for color targeting orto define a desired chromaticity. In some embodiments, the lightsource's chromaticity is within a distance less than 5e-3 from the whitelocus, when computed with the 1964 10° CMFs.

Alternatively, in a specific application, the target chromaticity isintentionally offset below the Planckian. For instance, the targetchromaticity may be defined by a specific CCT and a specific distancebelow-Planckian (such as Duv=1e-3, 2e-3, 3e-3, 5e-3, 1e-2). In someembodiments, the light source's chromaticity is within a distance lessthan 5e-3 from this target chromaticity, when computed with the 1964 10°CMFs. Some embodiments are methods to target a light source chromaticityaccording to these principles.

In various embodiments, emitted light has a “normal” CCT (depending onthe application, the CCT could be in the range 2000K-7000K, 2700K-6500K,in the range 2700K-5000K, in the range 3000K-5000K, in the range2700K-3000K, or substantially at 2700K or 3000K or 3500K or 4000K or5000K or 6500K) and having a large amount of violet light (in the range20%-70%, 25%-50%, 30-40%, or substantially 10%, 15%, 20%, 25%, 30%, 35%,40%, 45%, 50%, 60%, 65%, 70%), while retaining a white lightchromaticity. In a variety of embodiments, the violet light has aspectral peak around 405 nm (i.e. substantially at peaking in the range400-410 nm, or at 400 nm, 401 nm, 403 nm, 404 nm, 405 nm, 406 nm, 407nm, 408 nm, 409 nm, 410 nm).

In various embodiments, the emitted light is characterized by a distanceDuv from a desired chromaticity which is less than a predeterminedvalue. In some embodiments, the desired chromaticity may lie on theBlackbody locus or on the CIE daylight locus. In some embodiments, thepredetermined value may be less than 15E-3, less than 10E-3, less than6E-3, less than 4E-3, less than 2E-3, less than 1E-3, less than 0.5e-3.In terms of the well-known MacAdam ellipses, a Duv distance of ±0.006 isapproximately equivalent to a 7-step MacAdam ellipse. Therefore, thepredetermined value may for instance correspond to a MacAdam ellipsewhich is less than 7 steps, 5 steps, 3 steps, 1 step.

In many embodiments, retaining a white chromaticity within the emittedlight is not trivial because, as the amount of violet light is raised(for instance to a violet fraction of 20-40%), the chromaticity tends todrift below the Planckian locus in the violet direction. To compensatefor this, in various embodiments, the amount of blue light in thespectrum of the emitted light is reduced. Further, as the human eye ismuch less sensitive to violet (e.g. 405 nm) than to blue (e.g. 450 nm),it takes a lot of violet light to achieve the same chromaticity balanceas would be obtained with relatively little blue light in a spectrum.Therefore, embodiments achieve a white chromaticity on the Planckianlocus with very little blue light and a large amount of violet light.This may be useful for applications such as bactericidal lighting, orcircadian-friendly lighting (for instance, SPDs having little blueradiation in the range 440-490 nm). In other cases, the presentteachings may however also be relevant to sources having little or noviolet light. For instance, some sources having very narrow bandwidths(such as sources having laser peaks) or an absence of radiation in awide wavelength range may likewise suffer from inaccurate predictionswith standard 2° CMF targeting regardless of their violet content—thismay happen because the SPD samples the CMFs in a region where they areinaccurate (which may be in the short-wavelength range or in antherrange, including crossover regions where two cone fundamentals crossover, such as around 460-470 nm or 540-560 nm). Therefore, the presentteachings regarding use of suitable CMFs and other chromaticity-matchingmethods may apply to general lighting and to display. In some cases,they apply to embodiments emitting an SPD having at least a spectralpeak with a FWHM less than 20 nm (or 10 nm or 5 nm) which carries atleast 5% of the SPD's power. In some cases they apply to embodimentsemitting an SPD having a low-radiation region, where low-radiationregion may be a wavelength region of at least 50 nm (or 30 nm or 80 nm)located in the visible range 400 nm-700 nm (or 450 nm-650 nm) such thatless than 5% (or 2% or 1% or 0.5%) of the SPD is present in thiswavelength range. Embodiments may include sources having a largediscrepancy (such as Duv>0.001, 0.003, 0.005, 0.01, or Dxy>0.001, 0.003,0.005, 0.01, 0.02) between chromaticities according to two distinctCMFs, for instance between 1931 2° CMFs and 1964 10° CMFs. Embodimentsmay include a method of color-targeting such SPDs.

FIG. 2a is prior art and shows a spectrum 202 having standard SPD with aCCT of 3000K formed of blue light spectrum 204, green light spectrum 206and red light spectrum 208. FIG. 2b illustrates a spectrum 210 havingthe same chromaticity, the same number of lumens as spectrum 202, buthaving a violet LED peak (violet light spectrum 212) instead of a blueLED peak (blue light spectrum 204). This SPD of spectrum 210 has aviolet fraction of 42% and, in one embodiment, is obtained by combiningspectra representative of a green silicate phosphor, a red nitridephosphor and a violet LED. In other embodiments, other phosphors havingsimilar spectra may be alternatively used. For example, in one or moreembodiments, the use of a green beta-sialon phosphor may be suitable.

In one embodiment, the reduction of blue light in the spectrum ofemitted light may be achieved in several ways. In one embodiment, thespectrum may be created with a violet pump die, a green phosphor and ared phosphor, but no blue phosphor. Alternatively, a notch opticalfilter which cuts off light in the blue range may be used. Such filterscan be absorbing filters or dichroic filters, or similar filters. Insome cases, a violet-green-red spectrum is combined with a filter tofurther cut off blue content. In some embodiments, the amount of blueradiation is not completely eliminated but merely reduced. For instance,blue radiation may originate from a phosphor or an LED or othersolid-state-lighting emitter, whose intensity is selected to achieve adesired violet fraction. This is shown on FIG. 17, where the amount ofviolet and blue radiation is traded off to achieve a constantchromaticity with a varying violet fraction. As shown in FIG. 17, therespective amount of blue and violet radiation can be traded off toachieve a desired chromaticity and a desired violet content. SPDs 1702and 1704 show the end points of this process, with near-maximal blueemission (1702) or violet emission (1704). Other embodiments along thecurve of FIG. 17 combine a violet emission and a blue emission.

In particular, some embodiments may include the use of very highefficiency GaN-based violet emitters on bulk GaN, as demonstrated byassignee in U.S. patent application Ser. No. 12/884,848, filed Sep. 17,2010, and Hurni15.

In one or more embodiment, the light source or sources are solid-statelight emitters. In some embodiments, a violet laser diode is usedinstead of a violet LED. In one or more embodiments, laser diodesprovide a narrow spectrum (which may be narrower than 0.1 nm or 0.5 nmor 1 nm or 2 nm, quantified as a full-width at half maximum or a fullwidth at 90% of maximum). In various embodiments, a narrow spectrum witha peak near 405 nm provides violet radiation at the peak efficiency forbactericidal effect, in contrast to an LED which may have emission tailsat shorter and longer wavelengths.

FIG. 3 shows a spectrum 302 having a laser line at 405 nm and a greenand a red phosphor. It is shown on log vertical scale as the very sharpviolet line would hide the rest of the spectrum in linear scale. Thespectrum 302 is on-Planckian with CCT=3000K, and has a very high violetfraction of 65%. The spectrum 302 is obtained by combining spectrarepresentative of a green silicate phosphor, a red nitride phosphor anda violet LED—although other phosphors having similar spectra would alsobe suitable. For instance, use of a green beta-sialon phosphor or ayellow or green garnet phosphor may be suitable.

Similarly, violet LEDs with improved properties having a narroweremission—typically peaking near 405 nm—can be used. Narrow emission canbe obtained by optimizing the epitaxial properties of the LED emitter.Although the spectra shown in this application are representative ofinorganic III-Nitride LEDs with InGaN quantum wells, other lightemitters (LEDs and lasers, inorganic and organic, various materialssystems) can be envisioned to emit violet light.

In the case of InGaN emitters, for instance, the active region of theLED comprises InGaN layers. By selecting the composition of these layers(amount of In and Ga), as well as their thickness, one can tune theemitter's emission wavelength to a desired value such as 405 nm, as isknown in the art.

In some embodiments, direct emission of green and/or red light may beused instead of a phosphor. For instance the light source may consist ofa violet emitter (LED or laser) combined with a green LED and a red LED;or a green phosphor and a red LED, or a green LED and a red phosphor.

In some embodiments comprising phosphors, the phosphors are directlyexcitable by the violet emitter.

FIG. 4a shows a violet LED optically coupled to a matrix of luminescentmaterials (such as phosphors). The light from the LED pumps thephosphors, to generate a spectrum such as those taught in thisdisclosure. FIG. 4b shows an alternate configuration with a laseroptically coupled to a luminescent material. FIG. 4c shows aviolet-green-blue system of direct emitters.

FIG. 5 shows a schematic cross-section of the epitaxial layers of anLED, including the n-doped GaN layers, the p-doped GaN layers and theactive layers. The active layers may contain InGaN and be configured toemit near 405 nm.

In some embodiments, the spectrum is on-Planckian when calculated withother color matching functions (CMFs) than the original CIE 1931 2°CMFs. Applicants have discovered that this may be desirable because the2° CMFs are inaccurate, especially at short wavelength. Experiments inour laboratories have demonstrated that using the 1964 10° CMFs yieldeda much better perceptual match of chromaticity; in other words, if wedesign a source having a large violet fraction to be on-Planckian (at agiven CCT) according to the 10° CMFs, this source has a perceivedchromaticity which is close to a blackbody radiator (i.e. a filamentlamp) at the same CCT. In contrast, if color targeting is performed with2° CMFs, the perceived chromaticity may have a pronounced pinkish tint.Besides the CIE 1964 10° CMFs, one skilled in the art will know to useother modern CMFs such as those developed by CIE TC 1-36 (which can bederived at any relevant viewing angle, including 2°, 10° and others, aswell as for specific age groups by taking into account the reducedshort-wavelength sensitivity caused by aging).

Resources on modern CMFs, and related data, can for instance be found athttp://www.cvrl.org/cmfs.htm. CMFs of interest for this inventioninclude the 1964 10° CMFs, and the 2005 2° and 10° CMFs (developed by TC1-36, and also called physiologically-relevant XYZ functions).

Given a set of CMFs (x, y z) and an SPD S, chromaticity is calculated asfollows: X=int(S·x), Y=int(S·y), Z=int(S·z), x=X/(X+Y+Z), y=Y/(X+Y+Z),z=Z/(Z+Y+Z). Here int( ) denotes the integral over wavelength.

FIG. 20 illustrates the difference between various CMFs. Plot 2000 showsthe third CMF z in four cases: 1931 2° (2001), 1964 10° (2002), 2005 2°(2003), 2005 10° (2004). The discrepancy in z has been found to largelydrive the discrepancy in some chromaticity predictions discussed in thisApplication, because z is the CMF which is most sensitive toshort-wavelength. FIG. 20 shows that, while all four z functions aredistinct, the 1931 2° function z stands out: it has a lower value atshort wavelength, i.e. in the range 400-430 nm, whereas the other threez functions are nearly identical in the range 400-430 nm. Form this, itcan be expected that the three other CMFs (namely 1964 10°, 2005 2°,200510°) will yield chromaticity predictions that tend to agree witheach other, especially when an SPD has a large amount ofshort-wavelength light, and which will disagree with chromaticitiescalculated using the 1931 2° CMFs. Accordingly, in some embodiments,either of these three CMFs can be used to target a chromaticity andobtain a perceptually-white SPD. Alternately, a suitable CMF for someembodiments may be a CMF whose z function has a value in the range0.15-0.25 at 405 nm (in contrast to the 1931 2° CMF z, which has a valueof about 0.1).

While the existence of various CMFs is known in the art, color targetingis customarily achieved with the 1931 2° CMFs. The prior art considersthis suitable, failing to realize that the differences in CMFpredictions are exacerbated, for instance, in the case of an SPD havinga large fraction of violet light. Some embodiments of the invention arecharacterized by SPDs having a large discrepancy between theirchromaticity according to 1931 2° CMFs and other CMFs.

FIG. 18a illustrates SPDs having varying violet contents (in the range390-420 nm) which have been targeted on-Planckian at 4000 K with 2°CMFs, and shows their distance from Planckian Dxy calculated with 10°CMFs. As the violet content increases, Dxy increases, showing that“nominally” targeted SPDs are off-color according to the 10° CMFcalculation (Dxy is negative, so a pinkish tint is predicted) and thatthis effect becomes significant for violet contents above 15%. For priorart SPDs having very low violet contents, the discrepancy between CMFsmay be tolerable, while it may be problematic for SPDs with a highviolet content. FIG. 18(b) shows the converse situation where the SPD istargeted with 10° CMFs and Dxy is calculated with 2° CMFs. Theconclusions are the same: an SPD with large violet content (more than15% or 20% or 25% or 30%) has a large discrepancy, and may appearoff-color according to 2° CMFs (Dxy is positive, so a greenish tint ispredicted) while it is properly targeted according to 10° CMFs.

Accordingly, some embodiments have a violet content, a Dxy (calculatedwith 1931 2° CMFs), and a Dxy (calculated by other CMFs, such as the1964 10° CMFs), which are given by the table below:

Violet Dxy Dxy content > (2°) > (other) < 15% 3E−03 1E−03 20% 5E−031E−03 25% 7E−03 1E−03 30% 1E−02 1E−03 35% 1E−02 1E−03

FIGS. 6a-6d illustrate targeting by various CMFs. FIG. 6a is an SPD at3500K, on-Planckian according to 2° CMFs. FIG. 6b is an SPD at 3500K,on-Planckian according to 10° CMFs. FIG. 6c is the (x-y) color spacecalculated with 2° CMFs, with the SPD of FIG. 6a shown as a square andthe SPD of FIG. 6b shown as a circle. FIG. 6d is the (x-y) color spacecalculated with 10° CMFs, with the SPD of FIG. 6a shown as a square andthe SPD of FIG. 6b shown as a circle. In both FIGS. 6c and 6d the blackcurve is the Planckian locus. SPD. 6 a is on-Planckian on FIG. 6cwhereas SPD 6 b is off-Planckian, and vice-versa in FIG. 6d . In FIG. 6d, SPD 6 a is off-Planckian by a very large amount, indicating a verylarge pink tint.

Therefore it appears that using the 2° CMFs for color targeting may notbe desirable, especially in some cases where the spectrum has a lot ofviolet light. To obtain a perceptual match (for instance, to a Blackbodyradiator at a given CCT), it may be advantageous to use the 10° CMFs, orother accurate CMFs. The development of improved CMFs is an ongoingprocess. Embodiments can make various uses of improved CMFs.

As illustrated in FIGS. 6a-6d , the distinction between various CMFs canbe expressed as follows. Consider a chromaticity specification (ortest), expressed as a target center chromaticity (for instance, on thePlanckian locus) and a tolerance such as a maximum distance from thetarget point (calculated for instance as a Cartesian distance in a colorspace such as (uv), (u′v′), (xy)). As shown in FIG. 6, an SPD may meetthe specification according to a set of CMFs but not another. Forinstance on FIG. 6b , the SPD is within a distance Dxy=<0.03 of thePlanckian (and also Dxy=<0.025, 0.02, 0.015, 0.01, 0.005) according tothe 10° CMFs [FIG. 6(d)]; on the other the same SPD is above a distanceDxy>=0.03 of the Planckian (and also Dxy>=0.025, 0.02, 0.015, 0.01,0.005) according to the 2° CMFs [FIG. 6(d)]. Accordingly, someembodiments meet a chromaticity specification according to desired CMFs(such as the 1964 10° CMFs) but not according to the 1931 2° CMFs.

Likewise, as shown in FIGS. 6a-6d , some embodiments have SPDs which aresubstantially off-Planckian according to the 2° CMFs but on-Planckianaccording to more desirable CMFs (including the 10° CMFs). Further, FIG.6c indicates that the SPD of FIG. 6b is substantially off-Planckian,whereas FIG. 6d indicates that the SPD if FIG. 6b is substantiallyon-Planckian.

In some embodiments, SPDs have a distance to the Planckian locus that issmaller when it is computed with 10° CMFs than when it is computed with2° CMFs—as is the case for the SPD on FIG. 6 d.

It should be appreciated that these considerations about the differencein chromaticity (between different sets of CMFs) can be especiallymeaningful for an SPD having large amounts of violet radiation, as isthe case of some embodiments, and as illustrated above.

While the above discussion focuses on SPDs targeted on-Planckian,off-Planckian targeting is also possible. In some embodiments, for anSPD which is perceptually slightly pinkish (corresponding to a slightlybelow-Planckian targeting) to be preferred. In such cases, the sameaspects are valid: given a desired chromaticity, the SPD may be targetedusing non-2° CMFs different from the 1931 2° CMFs, and the chromaticitydistance to the desired target may be larger according to 2° CMFs thanto the non-2° CMFs.

Chromaticity distances may be expressed in a variety of color spaceslike (xy) and (uv), and values can be converted between these. Forinstance, referring to FIG. 6, the SPD of (b) is separated from thePlanckian locus (according to 2° CMFs) by about Dxy=0.030 and Duv=0.015,according to the conversion factor discussed earlier.

FIG. 7 is an experimental measurement of an embodiment, illustrating 10°targeting. This spectrum has a CCT of 4000K, a CRI Ra>80, and ison-Planckian according to the 1964 10° CMFs. It uses a 405 nm LED andthe following phosphors: (Ba,Sr)2SiO4:Eu (BSS) and (SrxCa1-x)AlSiN3:Eu(SCASN).

In many embodiments, it may be necessary to use appropriate CMFs tocreate embodiments with the intended chromaticity perception.Alternately, embodiments may be obtained by aid from perceptualexperiments rather than from calculations of chromaticity. In somecases, a spectrum is obtained by matching the perceived chromaticity ofanother light source (for instance, a filament lamp of a desired CCT oranother light source like a ceramic metal halide source, which may beon- or off-Planckian). This process may be accomplished by selecting anexisting light source, determining its chromaticity with CMFs which aredifferent from the 1931 2° CMFs, and matching this chromaticity,according to the same CMFs, with an embodiment. Alternatively, the matchmay be achieved by a visual match, where the embodiment's spectrum isconfigured such than a human subject considers the two perceivedchromaticities as substantially similar or identical.

Although the present examples are on-Planckian, slight deviations from adesired chromaticity are acceptable. For example, an embodiment may bewithin a chromaticity Duv distance less than 6E-3 (or 4E-3, or 2E-3, or1E-3) from the Planckian locus. This Duv distance may be calculated with1964 10° CMFs.

Some embodiments of the invention are lighting systems emitting aspectrum taught herein. Such systems may be lamps or fixtures ordisplays. They may comprise optical elements. For instance, a lamp maycomprise an optic (directional or diffuse), a fixture may comprise awaveguide. Some embodiments take into account the transmission of suchoptical elements, such that the chromaticity of interest is obtained forthe final light emitted by the system. For instance, if a lamp uses anoptic which absorbs some violet light, the lamp may comprise an LEDsource having a slightly off-chromaticity SPD (with an excess of violet)to compensate for said absorption, such that the final emitted SPD ison-chromaticity.

In some embodiments, care is taken to use optical elements having lowviolet absorption. For instance, PMMA, PMMI or glass may be preferredmaterials. In some embodiments, less than 10% (or 5%, 2%, 1%) of thelight emitted by the light-emitter is absorbed in the optical elements.

In some embodiments, care is taken to avoid the use of materialscontaining fluorescent whitening agents, which can unwantedly absorbviolet light and fluoresce blue light.

Color Rendition

Besides chromaticity, embodiments are distinguished by their colorrendition. One may expect that, with a large blue spectral gap, colorrenditions (such as CRI Ra or R9) may be very poor. However, it wasdiscovered that it was possible to obtain unexpectedly high values of Raand R9. In particular, use of a long-wavelength red phosphorsubstantially improved R9.

Some embodiments have a large violet fraction while maintaining Ra>80and R9>0. Based on our discovery, a series of spectra which met thesecriteria were generated by combining the spectrum of a violet pump LEDat 405 nm with the spectra of green and red phosphor having various peakwavelengths.

FIG. 8 shows an experimental embodiment with a CCT of 3000 K, Ra=85,R9=85, and a violet fraction of 16%. This spectrum uses a violet LED, a524-silicate green phosphor and a 650-CASN red nitride phosphor.

FIG. 9 shows color metrics versus CCT for a series of embodiments, allon-Planckian with 10° CMFs. The corresponding SPDs have been configuredto maximize their violet fraction while keeping Ra>80. However, by usinga slightly different violet emitter (such as a laser) and otherphosphors, even higher violet fractions can be envisioned. The examplesshown here are merely illustrative of possible values, and theiroptimization is of course possible. In general, as CCT increases, themaximum violet fraction increases.

It is possible to reach even higher values of color rendition.Accordingly, some embodiments have a large violet fraction whilemaintaining Ra>90 and R9>90.

FIG. 10 shows color metrics versus CCT for another series ofembodiments, all on-Planckian with 10° CMFs. These demonstrate R9>90 andRa>90. Similar comments apply as to those of FIG. 9.

Even higher values of color rendition are also possible, for instanceR9=95. Besides, embodiments can reach a high value of the TM-30 redrendering metric Rfh1 (e.g. Rfh1>50 or 80 or 90 or higher).

Some embodiments have applications in the medical field. In hospitals,the quality of light is sometimes evaluated using the COI index which isindicative of the color rendition of skin with various hemoglobinlevels. In particular, some standards require that lamps in hospitalshave a specific range of CCT and COI. To comply with AS 1680.2.5requirements for the reliable diagnosis of cyanosis, the COI should be3.3 or lower and the lamp correlated color temperature should be between3300 K and 5500 K. Embodiments of the invention meet these targets whilealso providing a high violet fraction.

FIG. 11 illustrates embodiments having a CCT in the range 3500-4800K anda COI below 3, together with a high violet fraction in the range25%-40%.

A specific example of such a spectrum is shown on FIG. 12. This spectrumhas the same chromaticity as a 5000 K Blackbody (calculated with 10°CMFs). Its CCT (calculated with the conventional calculation, based on2° CMFs) is 4800 K. It has Ra>90, R9>95, COI=2.7, Rf=70, Rfh1=80, and aviolet fraction of 36%. The spectra whose color metrics are shown onFIGS. 10-11 are similar to this spectrum, with slight variations in theintensity and peak position of the phosphors to match various CCTs.

This violet content can also be expressed in terms of violet watts (inthe range 390-420 nm) per lumen of light: the spectrum has 2 mW/lm ofviolet light. This value is high compared to a conventional lightsource. A blackbody at 5000 K has 0.3 mW/lm of violet light.

At other CCTs, other embodiments are also distinguished by a high ratioof violet mW to lumens. This is illustrated on FIG. 13.

FIG. 13 shows mW/lm (where the mW are the total violet watts computed inthe range 390-420 nm) for sources at various CCTs. The dashed line showsBlackbody radiators. They all have a low mW/lm, always less than 0.4.The full line shows embodiments of the invention (the correspondingspectra are the same which underlie FIGS. 10 and 11). These embodimentsare all on-Planckian (with 10° CMFs), with Ra>90 and R9>90. They aredistinguished by high mW/lm, always above 0.5 (and even above 0.7). ForCCTs in the range 3500-5000 K (which is relevant for medicalapplications), these embodiments have more than 1 mW/lm. In general, theembodiments of FIG. 13 have more than 5 times the amount of violet mW/lmthan does a Blackbody radiator at the same CCT.

Further, although no standard blue-based white LEDs are shown on FIG.13, they would have a much smaller violet mW/lm figure-of-merit thaneven Blackbody sources, since they hardly contain any violet light. Forinstance a typical blue-based white LED at 3000 K has less than 0.01mW/lm of violet light.

As has previously been mentioned, different violet ranges (or evenweighing by a violet bactericidal action spectrum) can be envisioned.This will change the values mentioned above, but will not change thegeneral trend that embodiments have much higher violet mW/lm thatstandard light sources.

Light Levels

Expressing the violet content in mW/lm enables one to predict the doseof violet light in a given application. For instance, if a light sourcehaving a violet content of 1 mW/lm emits 1000 lm and illuminates asurface of 1 square meter (i.e., the source has an illuminance of 1000lux), the violet flux is 1 W/m2.

In various embodiments, light sources emit about 1000 lm (or 500 lm,1500 lm, 2000 lm, etc. . . . ) of light. They have violet contents inthe range 0.5-3 mW/lm. Further, they may illuminate an area of about 0.1m2 to 1 m2 to 3 m2 (for instance, by placing a 10-degree beam source ata distance of less-than-one meter to a few meters from the illuminatedsurface). Depending on these configurations, a variety of violet W/m2can be achieved as needed for bactericidal effects.

Table 1 below shows a few examples, for a light source emitting 1000 lm.In this case, the violet irradiance ranges from about 0.17 W/m2 to 30W/m2.

lm violet mW/lm spot area (m²) violet W/m² 1000 0.5 0.1 5 1000 0.5 1 0.51000 0.5 3 0.17 1000 1 0.1 10 1000 1 1 1 1000 1 3 0.33 1000 2 0.1 201000 2 1 2 1000 2 3 0.67 1000 3 0.1 30 1000 3 1 3 1000 3 3 1

By increasing the source lm, higher values can be achieved, for instance100 W/m2.

In various embodiments, the source illuminates a surface with a violetirradiance of at least 0.5 W/m2 (or 1, 2, 5, 10, 20, 50, 100 W/m2). Insome embodiments, the violet irradiance is in the range 1-50 W/m2 or inthe range 1-10 W/m2.

Some embodiments are methods of using a source described in thisapplication, where the method comprises illuminating a surface forbactericidal effects with a selected violet irradiance. The method maycomprise suppressing a bacterial population with a selected suppressionrate.

As mentioned above, a common goal of LED lighting is to increase LER.One skilled in the art of LED lighting would typically not design an LEDwhose spectrum has such a large amount of violet light. Indeed, thehuman eye is much less sensitive to violet light than it is to bluelight. As a result, when the amount of violet light in a spectrum isincreased, the luminous efficacy of radiation (LER) of the resultingspectrum decreases. FIG. 17 shows the LER of a variety of LED spectraversus violet fraction (in the range 390-420 nm). As the violet fractionis increased, the LER decreases from 337 lm/W (for 0.5% violet in theSPD) to 257 lm/W (for 25% violet light in the SPD). FIG. 17 shows thatby varying the amount of violet and blue radiation a desiredchromaticity and violet fraction can be achieved.

Dynamic Mode

In some embodiments emitted SPD may vary. In one or more embodiments, alighting system comprises a first source which emits pure violet lightand a second source which emits a spectrum having green and red light.The latter source may be a violet-pumped LED with a green and a redphosphor, but with a small violet fraction.

Such dynamic embodiments (where the spectrum can be modified or tuned)may be formed using the teachings of U.S. patent application Ser. No.14/531,545. This includes multiple emitters including LEDs at variouswavelengths (including violet LEDs) and phosphors, whose power may bevaried to modify a spectrum.

When the two light sources are on, the system emits white light with adesired chromaticity (for instance, on-Planckian with 10° CMFs). Whenonly the violet source is on, the system only emits violet light. Thefirst mode may be used when users are present and/or at a predeterminedtime; the second mode may be used for disinfection/bactericidal effectsonly, when no user is present in the room and/or at a predeterminedtime. This reduces the energy consumption of the system, by onlyproviding the bactericidal effect. For instance, in a system whoseviolet fraction is 50% (in white-light mode), the energy consumption maybe about halved when only the violet emitters are present.

In various embodiments, a switch between the white-light mode and theviolet-only mode may be triggered by a variety of factors including:presence/movement detectors, time of day, computer algorithms based onmachine learning to infer the presence of a user, and other methodsknown in the art of dynamic lighting.

FIG. 14. shows how the spectrum of FIG. 12 can be obtained by combininga direct violet LED spectrum (dashed line) with a second spectrum havinga violet pump LED, a green phosphor and a red phosphor (full line). Inthis example, the second spectrum is not white—it is significantlyabove-Planckian; the combination of this spectrum with the violetspectrum yields the spectrum of FIG. 12 which is on-Planckian (whencalculated with 10° CMFs).

In other embodiments, the two light sources are substantially white buthave differing violet contents. Teachings of this invention can be usedto match the chromaticity of the two sources.

Emitters Selection

In various embodiments, a light source includes one or more violet pumpLEDs, as well as LEDs at other wavelengths (for instance blue, green,red), and phosphor materials emitting at various wavelengths (includingblue, green, red). In some embodiments, the violet pump LEDs arecombined with LEDs emitting at a longer wavelength (various combinationscan be used, for instance, violet LED pumping phosphor plus direct blueLEDs, or direct violet LEDs plus blue LEDs pumping phosphors, or violetLEDs pumping phosphors and blue LEDs pumping phosphors). In one or moreembodiments, a light source only includes violet pump LEDs that areconfigured to pump phosphors. U.S. patent application Ser. No.14/531,545 discloses various systems and methods for combining LEDS andis herein incorporated by reference.

In one embodiment, a light source may include a violet pump emitter andphosphors. The emission peak wavelength for the pump may be in the range400-410 nm, or in the range 403-407 nm. The pump may be an LED or laserdiode. This embodiment may be advantageous in some cases. For instance,use of only one type of light source (only violet LEDs for instance)means that the driving electronics are simple: standard one-stagedrivers can be used to drive the light sources. This enables a cheap androbust system. The reliability is controlled by the reliability of theviolet LEDs, so that drift of chromaticity over time may be good.Further, if very-efficient violet LEDs are used, this may provide anefficient configuration. If the phosphors are present over all theviolet LEDs, the light source may have a color-uniform appearance whenpowered, which can reduce the need for color mixing in a lightingsystem.

In other embodiments, a light source may include a violet emitter and ablue (or cyan or green) emitter, and some phosphors. The phosphors maybe pumped by the violet LED and/or the blue LED. This embodiment may beadvantageous in some cases. It may enable a tunable light source, wherethe power feeding the violet emitter and the blue emitter are varied tomodify the emitted spectrum. The blue LED may pump all the phosphors,which may minimize the Stokes shift and provide high efficiency. Theviolet LED may by a highly-efficient LED, which is suited to pump someor all the phosphors. The light source may be configured to have adesired white chromaticity at a given ratio of electrical powers drivingthe violet and blue LEDs.

Further, a light source may include two sub-sources: a violet emitterwith a first set of phosphors (source 1) and a blue emitter with asecond set of phosphors (source 2). This embodiment may be advantageousin some cases. For instance, the chromaticities of source 1 and source 2may be identical or substantially similar. In this case, the lightsource may be tuned between the two sources without the user noticing achange in chromaticity. This may enable a seamless switch frombactericidal mode to standard lighting mode (which may be moreenergy-efficient). The teachings of this invention may help ensure thatboth sources have a perpetually-similar chromaticity, for instancebecause they are color-targeted with an adequate set of CMFs.

In one embodiment, a light source may include a first phosphor emittingsubstantially green (or green-cyan-yellow) light and a second phosphoremitting substantially red (or orange-red-infrared) light.

Suitable classes of first phosphors with an emission peak between 500 nmand 550 nm include silicates or fluorosilicates doped with Eu2+;chalcogenides doped with Eu2+; nitridosilicates, oxynitridosilicates,oxynitridoaluminosilicates or beta-sialons doped with Eu2+ andcarbidooxynitridosilicates doped with Eu2+. Specific non-limitingexamples of suitable first phosphors include:

-   -   (Ba,Sr)₂SiO₄:Eu²⁺ (a typical formulation of “BOSE”)    -   (Mg,Ca,Sr,Ba,Zn)₂SiO₄:Eu²⁺ (a broader formulation of “BOSE”)    -   (Sr,Ca,Ba)(Al,Ga)₂S₄:Eu²⁺    -   Eu_(x)(A1)_(6-z)(A2)_(z)O_(y)N_(8-z)(A3)_(2(x+z−y)), where        0≤z≤4.2; 0≤y≤z; 0<x≤0.1; A1 is Si, C, Ge, and/or Sn; A2 is Al,        B, Ga, and/or In; A3 is F, Cl, Br, and/or I    -   M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy−2w/3)C_(xy)O_(w-v/2)H_(v):        A and    -   M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy−2w/3-v/3)C_(xy)O_(w)H_(v):A,    -   wherein 0<x<1, 0y<1, 0≤z<1, 0≤v<1, 0<w<1 x+z<1, x>xy+z, and        0<x−xy−z<1, M(II) is at least one divalent cation, M(I) is at        least one monovalent cation, M(III) is at least one trivalent        cation. H is at least one monovalent anion, and A is a        luminescence activator doped in the crystal structure.

Suitable classes of second phosphors with an emission peak between 600nm and 670 nm include nitridosilicates doped with Eu2+;carbidonitridosilicates doped at least with Eu2+; chalcogenides dopedwith Eu2+ and oxides, oxyfluorides or complex fluorides doped with Mn4+.Specific non-limiting examples of suitable second phosphors include:

(Sr,Ca)AlSiN₃:Eu²⁺ (a typical formulation of “SCASN”)

(Ba,Sr,Ca,Mg)AlSiN₃:Eu²⁺ (a broader formulation of “SCASN”)

(Ba,Sr,Ca,Mg)_(x)Si_(y)N_(z):Eu²⁺ (where 2x+4y=3z)

The group:

Ca_(1-x)Al_(x−xy)Si_(1-x+xy)N_(2-x−xy)C_(xy):A  (1);

Ca_(1-x−z)Na_(z)M(III)_(x−xy−z)Si_(1-x+xy+z)N_(2-x−xy)C_(xy):A  (2);

M(II)_(1-x−z)M(I)_(z)M(III)_(x−xy−z)Si_(1-x+xy−z)N_(2-x−xy)C_(xy):A  (3);

-   -   wherein 0<x<1, 0<y<1, 0≤z<1, 0≤v<1, 0<w<1 x+z<1, x>xy+z, and        0<x−xy−z<1, M(II) is at least one divalent cation, M(I) is at        least one monovalent cation, M(III) is at least one trivalent        cation. H is at least one monovalent anion, and A is a        luminescence activator doped in the crystal structure.

(Na,K,Rb,Cs)₂[(Si,Ge,Ti,Zr,Hf,Sn)F₆]:Mn⁴⁺

(Mg,Ca,Zr,Ba,Zn) [(Si,Ge,Ti,Zr,Hf,Sn)F₆]:Mn⁴⁺

(Mg,Ca,Sr,Ba)(S,Se):Eu²⁺

(Na,K,Rb,Cs)₂[(Si,Ge,Ti,Zr,Hf,Sn)F₆]:Mn⁴⁺

(Mg,Ca,Zr,Ba,Zn) [(Si,Ge,Ti,Zr,Hf,Sn)F₆]:Mn⁴⁺

3.5MgO.0.5MgF₂.GeO₂:Mn⁴⁺

Sr[LiAl₃N₄]:Eu²⁺.

Embodiments may make use of a first phosphor with an emission peakbetween 500 nm and 550 nm and a second phosphor with an emission peakbetween 600 nm and 670 nm. Optionally, one or more additionalphosphor(s) may be used as needed to optimize the luminous flux or thecolor rendering properties of the LED. The additional phosphor(s) mayhave an emission peak between 500 nm and 670 nm, or between 550 nm and600 nm. Examples of suitable classes of additional phosphors includethose of the aforementioned first and second phosphors classes emittingat different peak wavelengths than the specific first and secondphosphors selected, plus garnets doped with Ce³+, nitrides doped withCe³+ and alpha-sialons doped with Eu²+. Some specific non-limitingexamples of such additional phosphors include:

(Y,Gd,Tb,La,Sm,Pr,Lu)₃(Sc,Al,Ga)₅O₁₂:Ce³⁺

(La,Y,Lu)₃Si₆N₁₁:Ce³⁺

(Lu,Ca,Li,Mg,Y) alpha-SiAlON doped with Eu²⁺ and/or Ce³⁺

Alternatively, the phosphors can be layered sequentially in layers orlaid out in a parallel fashion (e.g. in a pattern of small patches)around the LED pump, as also known in the art.

One skilled in the art will know how to select phosphors with the properpeak wavelengths, and adjust the amount of each phosphor in the phosphorblends, layers or patterns in order to target any given color point ofinterest, obtainable per the color mixing rule as long as it lies withinthe region subtended by the color points of each phosphor and the LEDpump in the CIE chromaticity diagram. Achieving LED spectra with goodcolor rendering properties is however not straightforward since theinfluences of different spectral components are highly non-linear, andthere are no simple rules but rather an element of art involved inobtaining desirable Ra and R9 values, for example. It is traditionallyassumed in the lighting industry that a white spectrum with good colorrendering for general lighting purposes (e.g. with a CRI value of 80 orhigher and an R9 value higher than 0) should have a substantial emissionin the blue wavelength region, especially for CCT values above 2500K.For instance, it has been first predicted by numerical modeling andlater demonstrated experimentally that SPDs with peaks around 450 nm,540 nm and 610 nm provide a CRI of 80 or greater when color-balanced onthe Planckian locus across the range of CCT values used in generallighting. As a consequence, the tri-phosphor fluorescent lamp technologywas developed based on those specific emission peak wavelengths. Since awhite bactericidal spectrum with chromaticity on or substantially on thePlanckian locus may need to have its emission between 440 nm and 480 nmreduced or suppressed, a related impact on the CRI value from thisspectral deficiency around the 450 nm wavelength (widely consideredcritical to CRI based on the aforementioned precedents) can bereasonably expected in comparison to typical white blue-pumped LEDscontaining the same green and red phosphors or white violet-pumped LEDscontaining a blue-emitting phosphor and the same green and redphosphors. Unexpectedly, we were able to obtain white bactericidal LEDsexhibiting a local minimum in their spectral power distribution (SPD)between 420 nm and 500 nm and color-balanced near the Planckian locuswith both Ra≥80 and R9≥0, and higher values, as shown in the examplesgiven herein.

The lighting apparatus disclosed here can be an LED package or module, asolid state lamp (including direct replacement lamps for incandescent,halogen or fluorescent lamps), solid state lighting (“SSL”) fixture,light engine (the light generating component of a fixture), backlightingunit etc. Whenever the word “LED” is used in the foregoingspecification, it is only meant as a generic example of such a lightingapparatus not limiting the scope of applicability of this invention.

An optional band-stop filter (also known as a notch filter) can be addedto the lighting apparatus described above, to suppress the blue part ofthe spectrum even further if necessary. Such filters are known in theart and can be custom ordered from a variety of commercial suppliers.

Bactericidal Effect

FIG. 15 shows experimental results of violet light on bacteria. FIG. 15shows the bacterial count of MRSA bacteria, cultured and deposited on aglass slide, over time. In the absence of light (“Control”) there is amild bacterial reduction with time due to natural bacterial death inthis medium (the drop is less than a factor of ten in 36 hrs). Theexperimental LED light source emits violet light peaking at 405 nm, andprovides a violet irradiance on the order of 5-10 W/m2 on the glassslides. In the presence of this violet light, very significant bacterialreduction is observed.

A fit of the bacterial suppression yields a population rateP=10{circumflex over ( )}(hrs/5). Therefore, there is 90% suppression(i.e. suppression by a factor of ten) in about five hours and 99%suppression (i.e. suppression by a factor of a hundred) in about tenhours.

Some embodiments provide suppression (or kill rate) of a bacterialpopulation of at least a factor of ten in a given amount of time, forinstance 1 hr, 2 hr, 4 hr, 10 hr, 12 hr.

Some embodiments provide suppression (or kill rate) of a bacterialpopulation of at least a factor of one hundred in a given amount oftime, for instance 1 hr, 2 hr, 4 hr, 10 hr, 12 hr, 15 hr, 20 hr, 24 hr.

FIG. 16 shows experimental results of white light on bacteria. FIG. 16is similar to FIG. 15, but the light source is white light according toan embodiment of the invention. It has a CCT of about 3800 K. Thisspectrum is not exactly on-Planckian; however, one skilled in the artwould know how to configure similar embodiments targeted to beon-Planckian (or at other desired chromaticities) according to theteachings of this disclosure. The lamp's SPD has 36% violet content inthe range 390-420 nm. The lamp has an input power of 9 W. It has a spotbeam with a 10° half-angle. It illuminates a surface (glass slides withbacteria) at a distance of 2 meters. It has an illuminance of about1,350 lm/m2 near normal incidence, and a luminous equivalent ofradiation of about 230. Therefore, the corresponding violet irradianceis about 2 W/m2.

FIG. 16 again shows significant bacterial suppression. A fit of thebacterial suppression yields a population rate P=10{circumflex over( )}(hrs/10). Therefore, there is 90% suppression (i.e. suppression by afactor of ten) in about ten hours and 99% suppression (i.e. suppressionby a factor of a hundred) in about twenty hours.

The lamp configuration in the experiment of FIG. 16 corresponds to anilluminance and a violet irradiance which can be achieved in practicallighting situations. For instance, a lamp with a higher wattage (e.g. 18W) could be placed at a distance of 3 m from a surface for disinfection(for instance, it may be a spot lamp on a ceiling track) and provide asimilar violet irradiance. This geometry and light level may be suitablein domestic lighting applications (for instance to disinfect a sink, orbathroom or kitchen surface) as well as health care applications(hospitals and others).

The present experimental data pertains to MRSA. However, otherbactericidal effects are expected, with kill rates of a similar order ofmagnitude, for other bacterial strains which include C. Difficile, E.Coli, S. Pyogenes.

While this description is made with reference to exemplary embodiments,it will be understood by those skilled in the art that various changesmay be made and equivalents may be substituted for elements thereofwithout departing from the scope. In addition, many modifications may bemade to adapt a particular situation or material to the teachings hereofwithout departing from the essential scope. Also, in the drawings andthe description, there have been disclosed exemplary embodiments and,although specific terms may have been employed, they are unlessotherwise stated used in a generic and descriptive sense only and notfor purposes of limitation, the scope of the claims therefore not beingso limited. Moreover, one skilled in the art will appreciate thatcertain steps of the methods discussed herein may be sequenced inalternative order or steps may be combined. Therefore, it is intendedthat the appended claims not be limited to the particular embodimentdisclosed herein.

What is claimed is: 1-5. (canceled)
 6. A light source for emittingemitted light having a spectral power distribution (SPD) comprising: aplurality of light emitters including at least two violet solid-stateemitters having different peak wavelengths; wherein said emitted lighthas a chromaticity which is within a Duv distance of less than 5E-3 fromthe Planckian locus, wherein the chromaticity is calculated using CIE1964 10° CMFs; and wherein at least 25% of the power within the SPD isin the range 380-430 nm.
 7. The light source of claim 6, wherein saiddifferent peak wavelengths are between 395-415 nm.
 8. The light sourceof claim 6, wherein at least one of said different peak wavelengths is400 nm, 405 nm, 410 nm, 415 nm, 420 nm, or 425 nm
 9. The light source ofclaim 6, further comprising at least one phosphor, and wherein saidemitted light comprises at least a portion of light from said pluralityof light emitters and from said at least one phosphor.
 10. The lightsource of claim 9, wherein said at least one phosphor comprises at leastone red phosphor and a green phosphor.
 11. The light source of claim 6,wherein said emitted light has a CCT with a range 2700K-6500 K.
 12. Thelight source of claim 6, wherein said at least two violet solid-stateemitters are LEDs or laser diodes.
 13. The light source of claim 6,wherein said emitted light has a CRI Ra above
 80. 14. The light sourceof claim 13, wherein said emitted light has a CRI Ra above 90 and a CRIR9 above
 90. 15. The light source of claim 6, wherein the emitted lighthas a COI below 3.3.
 16. The light source of claim 6, wherein the SPD ischaracterized by a ratio of power in the range 390-420 nm to lumenswhich is above 0.5 mW/lm.
 17. The light source of claim 6, wherein thelight source is further configured to emit a second emitted lightcharacterized by a second SPD.
 18. The light source of claim 17, whereinsaid light source switches between emitting said emitted light and thesecond emitted light.
 19. The light source of claim 17, wherein saidsecond emitted light is characterized by a second chromaticity and asecond distance to the Planckian, Duv2, calculated using 1931 2° CMFs,wherein Duv2 is greater than 5E-3.
 20. The light source of claim 19,wherein said second emitted light is substantially pure violet light.21. A method of reducing bactericidal counts, the method comprising:powering a light source to emit emitted light having a chromaticity,said light source comprising a plurality of light emitters including atleast two violet solid-state emitters having different peak wavelengths,and at least one phosphor, wherein said chromaticity is within a Duvdistance of less than 5E-3 from the Planckian locus, wherein saidchromaticity and said Duv are calculated using CIE 1964 10° CMFs; andconfiguring said light source to illuminate a surface with said emittedlight to reduce a bacterial count by at least a factor of ten in twelvehours.
 22. The method of claim 21, wherein said different peakwavelengths are between 395-415 nm.
 23. The method of claim 21, whereinthe light source emits a second emitter light having a secondchromaticity and a second distance to the Planckian Duv2, calculatedwith the 1931 2° CMFs, and Duv2 is larger than 5E-3.
 24. The method ofclaim 21, wherein the surface receives a violet irradiance in the range390-420 nm of at least 1 W/m2.
 25. The method of claim 21, wherein thesource has a CRI Ra above 80.